Dyeing compositions



i nitd States company No Drawing. Filed Oct. 14, 1960, Ser. No. 62,551Claims priority, application Great Britain Oct. 23, 1959 13 Claims. (Cl.8-93) This invention relates to dyeing compositions suitable for use inhousehold washing machines.

According to one aspect of the invention, there is provided a dyeingcomposition in paste form comprising a substantially anhydrous mixtureof a dyestutf having an affinity for a textile fibre, or of a mixture ofdyestuffs having an afiinity for two or more different textile fibres,for example a union dyestutf mixture, and a liquid nonionic detergent.

According to another aspect of the invention, there is provided a dyeingcomposition in powder or granular form comprising a mixture of adyestuif having a affinity for a textile fibre, or of a mixture ofdyestufis having an afiinity for tWo or more different textile fibres,for examplc a union dyestuff mixture, and one or more nonionicsupplemented by one or more anionic detergents if desired, whichdetergent or detergents may either be solid per se or, if liquid, may becaused to assume solid characteristics.

The dyeing compositions of the invention may contain, if desired, asmall proportion of an optical whitening agent for the purpose ofbrightening pastel shades, for example the commercial product sold by1.0.1. Limited under the trade name Fluolite M1. or the commercialproduct sold by Hickson & Welch Limited under the trade name PhotineC33. The dyeing compositions may also contain agents which assist thedyeing action of the compositions, such as for example, sodium chlorideor anhydrous sodium sulphate. These agents may also assist the detergentaction of the composition.

The dyeing compositions when in paste form may contain, if desired, athickening agent for the paste, for example, carboxymethyl cellulose orstarch, which agent may also act as a suspending medium for soil removedfrom a treated textile material. The thickening agent is preferably onewhich is soluble both in the liquid nonionic detergent (to impartviscosity to the paste) and in water, such as for example a polyglycolether having a molecular weight greater than 1,000. Alternatively, thenon-ionic detergent may itself act as a thickening agent.

The dyeing compositions may also contain, if desired, a small proportionof sodium hexametaphosphate for the purpose of preventing the formationof precipitates due to the hardness of the Water when dyeing at hightemperatures. The proportion of sodium hexametaphosphate should not beless than 0.0001% (1 part per million) by weight of the quantity ofwater to which the composition is to be added and is preferably not lessthan about 0.0005% (5 parts per million).

By employing the dyeing compositions of the invention, the unexpecteddiscovery has been made that it is possible to carry out in a singleoperation in a Washing machine the simultaneous deterging and dyeing oftextile articles, for example curtains or clothing, made from the sameor diffrent textile fibres such as cotton, woolen, silk, viscose,acetate rayon and nylon fibres. This property of the compositions of theinvention is unexpected, since many commercial detergents restraindyestuffs from dyeing fabrics, with the result that the effect of mixingmany commonly used detergents and dyestuffs is, normally, to reduce theaflinity of the fabric for the dyestuff, hence giving a lighter shade ofdyeing. However, the compositions of the invention enable dyeing andwashing to be performed at the same time, the resulting dyeing beingcomparable in strength with a dyeing carried out under similarconditions using the same quantity of dyestuff without a detergent beingpresent.

It has been found that contrary to expectations the presence of water inthe dyeing compositions in paste form of the invention exercises adeleterious influence on the physical properties of the paste. However,a paste of the required consistency may be obtained by the use of asubstantially anhydrous liquid non-ionic detergent. This point is ofimportance in the filling of containers with the composition and in thedispensing of the composition into a dye-bath, and also in the storageof the composition.

When the dyeing compositions are prepared with anionic detergents, it isnecessary to alter the amount of dyestuff in the composition to obtainthe same effect as a similar composition containing a non-ionicdetergent. This alteration in the proportion of dyestuff in thecomposition is necessary to overcome the competition for active sites onthe material between the detergent and the dyestulf.

Instead of using a single non-ionic detergent in the dyeing composition,there may be employed a mixture of non-ionic and anionic detergents,particularly a mix ture containing a major proportion of a non-ionicdetergent and a minor proportion of an anionic detergent, for example asulphonated alkyl benzene. Such mixtures have been found to showimproved detergency over that obtained by either detergent used aloneand cause comparatively little effect on the exhaustion of the dyestuff.

Of the liquid non-ionic detergents which may be employed in the dyeingcompositions of the invention, it is preferred to use an alkyl arylpolyethylene glycol ether, particularly an ether having the structuralformula:

R-Q-o oniornmnn RO (CH CH O H wherein R is a straight chain hydrocarbonradical containing from 10 to 16 carbon atoms, preferably 12 carbonatoms, and x has a value of from 10 to 30, preferably 20. Still furtherpreferred liquid, non-ionic detergents which may be employed in thecompositions are polyethylene glycol esters of fatty and resin acids (itbeing recognized in the art that the chain hydrocarbon radical containsnot less than 12 carbon atoms), e.g. those sold by Atlas Powder Company(U.S.A.) under the trade name Renex, and polyglycol sorbitan esters offatty acids having H.L.B. (hydrophilic/lyophilic balance) numbers (asdefined by Griflin, J. Soc. Cosmetic Chem, 1949', 1, 311) of from 8 to20.

The non-ionic detergents exemplified above are either liquids or softwaxy solids at room temperature. In order therefore to prepare apowdered or granulated dyeing composition, it is necessary to convertthese detergents into a solid form. This may be done by adding to thedetergent a suflicient quantity of an inorganic salt, such as forexample sodium chloride, to produce a solid product. The free flowingproperties and rapid solubility characteristics of a solid productobtained in this manner may be improved by granulation. However, forconvenience in use, it is preferred to convert the detergent, whenliquid, into a solid form by mixing with an absorbent solid such as forexample, finely divided silica (for example the product sold in theUnited Kingdom by Bush, Beach & Segner Bayley Limited under the tradename Aerosil), fullers earth, or calcium silicate. The anionicdetergents employed, if liquid, may be converted into a solid form in asimilar manner.

Instead of converting the liquid or waxy detergent into a solid form inthe manner described above, there may be employed in the formulation ofthe compositions of the invention the crystalline concretions formedbetween the non-ionic detergent and urea, for example the product soldby the Atlas Powder Company (U.S.A.) under the trade name Renex 25,which product is the solid concretion product formed from urea and apolyoxyethylene ester of tall oil averaging 16 oxyethylene groups permolecule.

Other compounds may also be included in the composition in minorproportions, preferably those which have the efiect of suspending soilin solution, for example carboxymethyl cellulose.

Advantageously, the composition should contain sufficient detergent togive a concentration of at least 0.02%, preferably 0.1%, by weight ofdetergent in the quantity of water to which the composition is to beadded. The amount of dyestuff present in the composition depends, ofcourse, on the depth of shade required for the dyed textile articles andthe quantity of textile articles to be dyed. In the case of the dyeingcompositions in paste form, the amount of dyestuif presentadvantageously does not exceed 150% by weight of the amount ofdetergent, since a larger amount of dyestuff would affect the physicalproperties of the paste. In the event of 150% by weight of dyestufi in apaste composition giving too deep a shade, a smaller amount of dyestuifmay be used, the balance being made up by a dyeing assistant, e.g.anhydrous sodium sulphate or sodium chloride. The amount of thickeningagent used in the dyeing composition is dependent upon the dyestufI(plus dyeing assistant if used)/detergent ratio and also upon theparticular dyeing assistant, if used, typical values for the amount ofthickening agent being given in the specific examples below.

In the following examples, which illustrate dyeing compositions inaccordance with the invention, all parts are by weight.

Example 1 4.25 parts of the dyestuif C.I. Direct Yellow 12 and 5.75parts of anhydrous glauber salts (or 2.3 parts of common salt) weremixed with 7.5 parts of the commercial product Lissapol NX and 0.66 partof polyethylene glycol 1500 and the resulting mass was ground to asmooth paste.

The paste obtained in the above manner was used to dye cotton goods inthe following manner.

The paste was added to approximately 7,000 parts (9 gallons) of watercontained in a suitable vessel or machine, e.g., a domestic washingmachine, in which the liquid can be suitably agitated and, preferably,can be simultaneously heated to its boiling point. The liquid wasagitated for a few seconds and then 454 parts of soiled cotton goodswere placed in the machine and the agitation and heating continued for afurther twelve minutes, after which the liquid was removed from contactwith the goods which were rinsed in cold water and dried in the usualmanner. The goods were strongly and levelly dyed a shade of yellow andsubstantially all soil had been removed.

Example 2 4.8 parts of the dyestufi C.I. Direct Blue No. 24, 5.25

parts of anhydrous glauber salts (or 2 parts common salt) and 7.5 partsof Lissapol NX were ground together to form a paste. This paste whenused to dye 454 parts of soiled cotton goods as described in Example 1yielded 5 a deep and level dyeing of clean material.

Example 3 A paste was prepared in the manner described in Example 1, the0.66 part of polyethylene glycol 1500 being replaced by 0.8 part ofethyl cellulose (viscosity grade 50).

Example 4 A paste was prepared in the manner described in Example 1, the0.66 part of polyethylene glycol 1500 being replaced by 2 parts of ablock copolymer of ethylene oxide and propylene oxide sold by WyandotteLimited (U.S.A.) under the trade name Pluronic F.68.

Example 5 Example 7 A paste was prepared as in Example 1, the 0.66 partof polyethylene glycol 1500 being replaced by 1.066 parts of sodiumcarboxymethyl cellulose.

Example 8 A paste was prepared as in Example 1, the 066 part ofpolyethylene glycol 1500 being replaced by 2.13 gms. of carragheen mossextract, e.g. the commercial product sold by J. W. Cummins & SonsLimited, under the trade name Carmoss.

Example 9 2.4 parts of the dyestuff Cl. Direct Blue No. 24, 8 parts ofanhydrous glauber salts, 7.5 parts of Lissapol NX and 0.4 part of anoptical whitening agent sold by Hickson and Welch Limited under thetrade name Photine 0.33 Liquid were thoroughly mixed by milling orgrinding together to form a paste. When 13.3 parts of the paste obtainedin the above manner were used in the manner described in Example 1,there were obtained pastel blue shades of good brightness on soiledmaterial.

Example 10 Apaste was prepared as in Example 1, the 7.5 parts ofLissapol NX being replaced by 7.4 parts of the commercial product Renex20.

Example 1] Example 12 A paste was prepared as in Example 9, the 7.5parts of Lissapol NX being replaced by the commercial product TexoforF.10 (an alkyl phenol polyglycol ether).

Example 13 A paste was prepared as in Example 9, the 7.5 parts ofLissapol NX being replaced by 7.5 parts of the commercial product Renex30.

Example 14 A paste was prepared as in Example 1, the 4.25 parts of thedyestuif C.I. Direct Yellow 12 being replaced by a mixture of 1.3 partsof the dyestuff C.I. Disperse Blue 7, 0.2 parts of the dyestufl? Cl.Disperse Yellow 8, 0.5 part of the dyestufi C.I. Acid Blue 5, 1.3 partsof the dyestuff Cl. Direct Blue 1 and 0.5 part of the dyestuff C.I.Direct Yellow 11.

The resulting paste dyeing composition was added to approximately 7,000parts of water contained in a domestic washing machine in which theliquid can be suitably agitated and, preferably, can be simultaneouslyheated to its boiling point. The liquid was agitated for a few secondsand then 450 parts of soiled cotton, woolen, silk, viscose, acetaterayon and nylon goods were placed therein and the agitation and heatingcontinued for 4 minutes. The heating was then continued with agitationfor seconds at 2 minute intervals until the goods had been immersed fora total of 20 minutes. The goods were then removed from contact with theliquid, rinsed in cold water and dried in the normal way. The goods weredyed a deep and level shade of green and all soil had been removed.

Example A paste was prepared as in Example 14, but the 7.5 parts ofLissapol NX were replaced by 7.5 parts of the commercial product Renex20.

Example 16 33 parts of the dyestulf 0.1. Direct Yellow 12, 17 parts ofthe dyestufi 0.1. Direct Yellow 11, 8 parts of the dyestuff CI. DisperseYellow I and 78 parts of anhydrous sodium sulphate were mixed, and partsof the resulting mixture were mixed with 30 parts of the commercialproduct Lissapol NX, to which had been added previously 140 parts ofsodium chloride. To the resultant paste 10 parts of finely dividedsilica, for example the commercial product sold in the United Kingdom byBush, Beach & Segner Bayley Limited under the trade name Aerosil, wereadded. The resulting powdered dyeing composition was then added toapproximately 45,000 parts of water contained in a domestic Washingmachine, in which the liquid can be suitably agitated and, preferably,can be simultaneously heated to its boiling point. The liquid wasagitated for a few seconds and then 900 parts of soiled cotton, woolen,silk, viscose, acetate rayon and nylon goods were placed therein and theagitation and heating continued for 4 minutes. The heating was thencontinued with agitation for 10 seconds at 2 minute intervals until thegoods had been immersed for a total of 30 minutes. The goods were thenremoved from contact with the liquid, rinsed in cold water and dried inthe normal way. The goods were dyed a deep and level shade of yellow andall soil had been removed.

Example 17 A powdered dyeing composition was prepared in the mannerdescribed in Example 16, the 30 parts of Lissapol NX and finely dividedsilica being replaced by 60 parts of the commercial product Renex (whichis the urea concretion of the product obtained by forming thepolyoxyethylene ester of mixed fatty and resin acids). The powderedcomposition was then used to dye and deterge 900 parts of soiled goodsin the manner described in Example 16 and yielded a deep and leveldyeing of clean material.

Example 18 2.6 parts of the dyestuff C.I. Disperse Blue 7, 0.5 part ofthe dyestufi C.I. Disperse Yellow 13, 1 part of the dyestutf Cl.Disperse Yellow 13, 1 part of the dyestuff C.I. Acid Blue 5, 2.6 partsof the dyestulf (11. Direct Blue 1, 0.5 part of the dyestuff 0.1. DirectYellow 11 and 2.8 parts of sodium chloride were mixed and 20 parts ofthe resulting mixture were mixed with parts of the commercial productBelloid MY (an ethylene oxide modified long chain aliphatic alcohol) and140 parts of sodium chloride as in Example 16. To the resultant paste 8parts of finely divided silica, for example the commercial prod- 6 uctsold in the United Kingdom by Bush, Beach & Segner Bayley Limited underthe trade name Aerosil, were added. The resulting powdered compositionwas then used to dye 900 parts of soiled goods in the manner describedin Example 16 and yielded a deep and level dyeing of clean material.

Example 19 A powdered dyeing composition was prepared as in Example 18,but using 60 parts of the commercial product Renex 25 instead of theBelloid MY and finely divided silica. The resulting powdered compositionwas then used to dye soiled goods in the manner described in Example 16and yielded a deep and level dyeing of clean material. 7

Example 20 A powdered dyeing composition was prepared as in Example 18,but there were also included in the composition 0.1 part of the opticalwhitening agent sold by Hickson & Welsh Limited under the trade namePhotine C. This composition yielded pastel blue shades of goodbrightness on soiled material.

Example 21 A powdered dyeing composition was prepared in the mannerdescribed in Example 20, the 0.2 part of Photine C being replaced by theoptical whitening agent sold by LC Limited under the trade name FluoliteM.P. The resulting composition yielded pastel blue shades of goodbrightness on soiled material.

Example 22 13.61 parts of the dyestuff Cl. Direct Red 81, 0.25 part ofthe dyestufi Cl. Direct Yellow 44, 5.75 parts of the dyestutf Cl.Disperse Red 1, 1.5 parts of the dyestufi C.I. Disperse Red 13, 50 partsof the commercial product Renex 25' and 112 parts of sodium chloridewere mixed and the resulting powdered composition was added to approximately 27,000 parts of hot water at about C.

1125 parts of soiled cotton, silk, viscose, acetate rayon and nylongoods were then added to the stirred mixture, and agitation wascontinued for 12 minutes. The result ing dyed goods were then removedand rinsed thoroughly and dried in the normal way. The goods: were dyeda deep and level shade of red and all soil had been removed.

The powdered dyeing composition described above may also be used to dyein a similar manner soiled woolen goods in which case the agitationshould be carried out intermittently for the period of 12 minutes.

Example 23 A powdered dyeing composition was prepared in the mannerdescribed in Example 22 with the addition of 0.5 part of sodiumhexametaphosphate to the dry mixture.

What is claimed is:

1. A method comprising concomitantly washing a fabric and dyeing thesame to a predetermined shade by immersing said fabric in a watersolution of an amount of dye suflicient to provide said shade and of awatersoluble non-ionic organic synthetic detergent, said dye beingsubstantially unaffected by the presence of said synthetic detergent.

2. A method as claimed in claim 1 wherein the dye does not exceed aboutby weight of the detergent.

3. A method as claimed in claim 1 wherein the detergent is employed inan amount to yield a concentration of no less than about 0.02% in saidwater.

4. A method as claimed in claim 3 wherein the dye and detergent aredissolved in the water as a mixture in particulate form.

5. A method as claimed in claim 3 wherein the dye and detergent aredissolved in the water as a mixture in paste form.

6. A method as claimed in claim 3 wherein the detergent is an alkyl arylpolyethylene glycol ether represented by the general formula:

RQOKDHZOHNMH RO (CH CH O H wherein R is a straight chain hydrocarbonradical containing from 10 to 16 carbon atoms and x is an integer in therange of from 10 to 30.

8. A method as claimed in claim 3 wherein the detergent is selected fromthe group consisting of a polyoxyethylene ester of a fatty acid having aradical containing not less than 12 carbon atoms, a polyoxyethyleneester of a resin acid having a radical containing not less than 12carbon atoms, and mixtures thereof.

9. A method as claimed in claim 3 wherein the detergent is apolyoxyethylene ester of tall oil.

10. A method as claimed in claim 3 wherein the detergent is combinedwith urea to form a solid coneretion product.

11. A method as claimed in claim 3 wherein said detergent is combinedwith an absorbent solid.

12. A method as claimed in claim 3 further comprising dissolving asupplemental anionic detergent in the water.

13. A method as claimed in claim 3 further comprising adding a dyeassistant to the water soluiton.

References Cited in the file of this patent UNITED STATES PATENTS1,970,578 Schoeller et al Aug. 21, 1934 2,582,868 Hausmann et al Jan.15, 1952 2,901,312 Audas Aug. 25, 1959 2,923,593 Olpin et al Feb. 2,1960 2,930,760 Gebhardt Mar. 29, 1960 2,950,165 Ha-dfield et al Aug. 23,1960 OTHER REFERENCES Soap and Chemical Specialties, September 1957,pages 5053.

1. A METHOD COMPRISING CONCOMITANTLY WASHING A FABRIC AND DYEING THESAME TO A PREDETERMINED SHADE BY IMMERSING SAID FABRIC IN A WATERSOLUTION OF AN AMOUNT OF DYE SUFFICIENT TO PROVIDE SAID SHADE AND OF AWATERSOLUBLE NON-IONIC ORGANIC SYNTHETIC DETERGENT, SAID DYE BEINGSUBSTANTIALLY UNAFFECTED BY THE PRESENCE OF SAID SYNTHETIC DETERGENT.